HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions

ABSTRACT

A fluoropropene composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane wherein the 2,3,3,3-tetrafluoropropene being present in an amount of 0.00001 to 1.0%. A method of producing the fluoropropene, methods for using the fluoropropene and the composition formed are also disclosed.

This application is a Continuation of International Application No.PCT/US2020/029690 filed on Apr. 24, 2020 and also is aContinuation-in-Part of U.S. application Ser. No. 17/270,654 filed onFeb. 23, 2021 which is a 371 of International Application No.PCT/US2019/057999 filed Oct. 25, 2019 that claims the benefit ofProvisional Application No. 62/750,991 filed Oct. 26, 2018.International Application No. PCT/US2020/029690 is acontinuation-in-part of International of PCT Application No.PCT/US2019/057999, filed on Oct. 25, 2019. The disclosures ofApplication Nos. PCT/US2019/057999, PCT/US2020/029690, Ser. No.17/270,654, and 62/750,991 are hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to tetrafluoropropene compositions andmethods for making and using the compositions and, in particular, to amethod for producing and using a product comprising1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3,3-pentafluoropropene(HFO-1225zc), and 2,3,3,3-tetrafluoropropene (HFO-1234yf) prepared from1,1,1,3,3-pentafluoropropane (HFC-245fa).

BACKGROUND OF THE INVENTION

The fluorocarbon industry has been working for the past few decades tofind replacement refrigerants for the ozone depletingchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) beingphased out as a result of the Montreal Protocol. The solution for manyapplications has been the commercialization of hydrofluorocarbon (HFC)compounds for use as refrigerants, solvents, fire extinguishing agents,blowing agents and propellants. These new compounds, such as HFCrefrigerants, HFC-134a and HFC-125 being the most widely used at thistime, have zero ozone depletion potential and thus are not affected bythe current regulatory phase-out as a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is anotherenvironmental concern in many of these applications. Thus, there is aneed for compositions that meet both low ozone depletion standards aswell as having low global warming potentials. Certain hydrofluoroolefincompositions are believed to meet both goals. Thus, there is also a needfor economical manufacturing processes that provide these compositions.

HFO-1234ze (CF₃CH═CHF) and HFO-1234yf (CF₃CF═CH₂), both having zeroozone depletion and low global warming potential, have been identifiedas potential refrigerants. U.S. Pat. No. 7,862,742 disclosescompositions comprising HFO-1234ze and HFO-1234yf. U.S. Pat. No.9,302,962 discloses methods for making HFO-1234ze. The disclosures ofU.S. Pat. Nos. 7,862,742 and 9,302,962 are hereby incorporated byreference in their entirety.

Catalytic dehydrofluorination of HFC-245fa in general produces a mixtureof both the E-isomer as well as the Z-isomer of HFC-1234ze. Depending onthe particular catalyst chosen, the amount of the Z-isomer can varybetween 15% to 23%. Dehydrofluorination in the liquid phase usingaqueous solutions of caustic or other strong bases also produces mixtureof both isomers. Although the ratio of the two isomers can be shiftedsomewhat by temperature, about 13% to about 15% of the Z-isomer istypically formed. As the E-isomer is the most useful for refrigerationapplications, after separation of the E-isomer from the Z-isomer, theZ-isomer is typically either isomerized to the E-isomer in a separatestep or converted back to 245fa through addition of hydrogen fluoride.Both alternatives require additional steps which add cost.

There is a need in this art for a process that can produce compositionsof HFO-1234ze and HFO-1234yf that minimizes or eliminates the need forpurification or separation steps for removing excess quantities ofHFO-1234yf. In particular, there is a need in this art for an economicalprocess that produces compositions comprising HFO-1234ze, HFO-1225zc andHFO-1234yf wherein the amount of HFO-1225zc and HFO-1234yf are eachgreater than zero and less than about 1 mole percent and wherein thetotal amount of HFO-1225zc and HFO-1234yf is less than about 1 molepercent.

BRIEF DESCRIPTION OF THE INVENTION

Described is a fluoropropene composition comprisingZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene,1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally1,1,1,3,3-pentafluoropropane. The 2,3,3,3-tetrafluoropropene beingpresent in an amount of 0.00001 to 1.0 mol %, the being present in anamount greater than 0 to 1.0 mole %, and the total amount of1,1,3,3,3,-pentafluoropropene and 2,3,3,3-tetrafluoropropene is greaterthan 0 and less than 1.0 mol %

In addition, the present disclosure includes a method of producing amixture of a fluoropropene of formula CF₃CH═CHF and a fluoropropene offormula CF₃CF═CH₂, comprising contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr2O3 or Cr/Ni on fluorinatedalumina, in the presence of an oxygen containing gas, to form a mixturecomprising Z-1,3,3,3-tetrafluoropropane, E-1,3,3,3,-tetrafluoropropene,1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene, and optionallyunreacted 1,1,1,3,3-pentafluoropropane. One embodiment the inventivemethod produces a useful composition without the need for purificationor separation steps including steps for removing excess quantities of2,3,3,3-tetrafluoropropene (HFO-1234yf) or 1,1,3,3,3-pentafluoropropene.

Further still, the present disclosure includes fluoropropenecompositions formed from the method of contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr2O3 or Cr/Ni on fluorinatedalumina, optionally in the presence of an oxygen containing gas.

In one embodiment, the inventive process produces a compositioncomprising HFO-1234ze(E), HFO-1225zc and HFO-1234yf and the compositionis useful as a refrigerant. In another embodiment, the compositioncomprises HFO-1225zc and a near azeotropic composition comprisingHFO-1234ze(E) and HFO-1234yf. In a further embodiment, the compositioncomprises a three component near azeotropic composition comprisingHFO-1234ze(E), HFO-1234yf and HFO-1225zc.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.01 to 1.0 mol %.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.1 to 0.9 mol %.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.2 to 0.4 mol %.

One embodiment relates to any combination of the foregoing wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.3 to 0.4 mol %.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition additionally optionally comprises one or moreof R-143a, R-152a, TFP (trifluoropropyne), R-1233xf, R-1233zd(E),R-1233zd(Z), R236fa, and at least one HFO-1234 isomer including at leastone of HFO-1234zc, HFO-1234yc and HFO-1234ye.

One embodiment relates to any combination of the foregoing wherein thesum total of the amounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E),and R-1233zd(Z) is between 0.001 mole percent and 2 mole percent, basedon the total fluoropropene composition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition includes R-1233zd(E) in an amount of 0.7 molepercent to 1.15 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition includes R-1233zd(Z) in an amount of 0.05 molepercent to 0.25 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition includes R-143a in an amount of 0.05 molepercent to 0.25 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thefluoropropene composition optionally comprises one or more of 1224yd,1224zc, 1326mxz, 113, 32, 23, trifluoropropyne, 356mff, 1326mxz,HFC-245fa and HFC-245cb.

One embodiment relates to any combination of the foregoing wherein thesum total of the amounts 1224yd, 1224zc, 1326mxz, 113, 32, 23,trifluoropropyne, 356mff, 1326mxz, HFC-245fa and HFC-245cb is between0.001 mole percent and 2 mole percent, based on the total fluoropropenecomposition.

One embodiment relates to any combination of the foregoing wherein thecomposition is near azeotropic.

Another embodiment of the invention relates to a method of producing amixture of a fluoropropene of formula CF₃CH═CHF and a fluoropropene offormula CF₃CF═CH₂, comprising:

-   -   contacting a mixture of 1,1,1,3,3-pentafluoropropane and        Z-1,3,3,3-tetrafluoropropene in the gas phase with a catalyst        comprising at least one catalyst selected from the group        consisting of fluorinated Cr₂O₃ or Cr/Ni on fluorinated alumina,        in the presence of an oxygen containing gas, to form a mixture        comprising Z-1,3,3,3-tetrafluoropropene,        E-1,3,3,3,-tetrafluoropropene, 2,3,3,3-tetrafluoropropene,        hydrogen fluoride, and optionally unreacted        1,1,1,3,3-pentafluoropropane        wherein the mixture includes 0.00001% to 1.00%        2,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein said mixture of 1,1,1,3,3-pentafluoropropane andZ-1,3,3,3-tetrafluoropropene comprises at least 7% by weightZ-1,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein said mixture of 1,1,1,3,3-pentafluoropropane andZ-1,3,3,3-tetrafluoropropene comprises at least 10% by weightZ-1,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein at least 94% by weight of the1,1,1,3,3-pentafluoropropane is converted to E-isomer of1,3,3,3-tetrafloropropene.

One embodiment of the invention relates to any combination of theforegoing wherein at least 98% by weight of the1,1,1,3,3-pentafluoropropane is converted to E-isomer of1,3,3,3-tetrafloropropene.

One embodiment of the invention relates to any combination of theforegoing and further comprising recoveringZ-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane, andrecycling Z-1,3,3,3-tetrafluoropropene, or a mixture ofZ-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane back tostep (a).

One embodiment of the invention relates to any combination of theforegoing wherein said hydrogen fluoride produced in step (a) isseparated and recovered.

One embodiment of the invention relates to any combination of theforegoing wherein said oxygen containing gas is oxygen, or air.

One embodiment of the invention relates to any combination of theforegoing wherein the mixture includes 0.1 to 0.5 mol %2,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein the mixture includes 0.2 to 0.4 mol %2,3,3,3-tetrafluoropropene.

One embodiment of the invention relates to any combination of theforegoing wherein the mixture includes 0.3 to 0.4 mol %2,3,3,3-tetrafluoropropene.

Another embodiment of the invention relates to any combination of theforegoing methods and to a fluoropropene composition produced by thesemethods.

A further embodiment of the invention relates to any combination of theforegoing embodiments and comprising a refrigerant compositioncomprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene,1,1,3,3,3-pentafluoropropene, and 2,3,3,3-tetrafluoropropene and atleast one member selected from the following groups:

-   -   (a) comprising one or more of R-143a, R-152a, TFP, R-1233xf,        R-1233zd(E), R-1233zd(Z) 1224yd, 1224zc, 1326mxz, 113, 32, 23,        trifluoropropyne, 356mff, 1326mxz, HFC-245fa, HFC-245cb 1234zc,        1234yc, 1234ye, 134a, 1225ye (Z and E), 114, 124, and 236fa,    -   (b) comprising one or more of R-143a, R-152a, TFP, R-1233xf,        R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32, 23,        trifluoropropyne, 356mff, 1326mxz, HFC-245fa and HFC-245cb,    -   (c) comprising one or more of HFC-1234ye, HFC-1243zf, HFC-32,        HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161,        HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc,        R1336mzz(E), propane, n-butane, isobutane, 2-methylbutane,        n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂, and CF₃I;    -   (d) combinations thereof.

One embodiment of the invention relates to a process for transferringheat, comprising:

providing an article;

contacting the article with a heat transfer media;

wherein the heat transfer media comprises the fluoropropene compositionof any combination of the foregoing embodiments and including a nearazeotropic composition produced by the inventive method.

One embodiment of the invention relates to a process for treating asurface, comprising:

providing a surface;

contacting the surface with a treatment composition;

wherein the surface includes a treatable material deposited thereon; andwherein the treatment composition comprises the fluoropropenecomposition of any combination of the foregoing embodiments.

One embodiment of the invention relates to any combination of theforegoing wherein the treatment composition substantially dissolves thetreatable material.

One embodiment of the invention relates to a process for forming acomposition comprising:

providing a solute; contacting the solute with a solvent;

wherein the solvent comprises the fluoropropene composition of any ofthe foregoing embodiments.

Another embodiment of the invention relates to a refrigeration system,comprising:

an evaporator; a condenser;

a compressor; an expansion device;

and a heat transfer media;

wherein the heat transfer media comprises the fluoropropene compositionof any combination of the foregoing embodiments and including a nearazeotropic composition produced by the inventive method.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims. The various embodiments ofthe invention can be used alone or in combinations with each other.Other features and advantages of the present invention will be apparentfrom the following more detailed description of the preferredembodiment, which illustrate, by way of example, the principles of theinvention.

DETAILED DESCRIPTION OF THE INVENTION

Described is a method of producing a mixture of a fluoropropene offormula CF₃CH═CHF, a fluoropropene of formula CF₂═CHCF₃ and afluoropropene of formula CF₃CF═CH₂, comprising contacting a mixture of1,1,1,3,3-pentafluoropropane and Z-,1,3,3,3-tetrafluoropropene in thegas phase with a catalyst comprising at least one catalyst selected fromthe group consisting of fluorinated Cr₂O₃ or Cr/Ni on fluoride alumina,optionally in the presence of an oxygen containing gas, to form amixture comprising Z-1,3,3,3-tetrafluoropropene,E-1,3,3,3,-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene,2,3,3,3-tetrafluoropropene, and, optionally, unreacted1,1,1,3,3-pentafluoropropane. Without wishing to be bound by any theoryor explanation, a higher contact temperature and/or increased length ofcatalyst contact time can cause formation of an increased amount of1,1,3,3,3-pentafluoropropene.

Certain dehydrofluorination reactions are well known in the art. Thedehydrofluorination of HFC-245fa has been particularly studied. Both gasphase and liquid phases processes are known. 1,3,3,3-tetrafluoropropene(HFO-1234ze) exists as both a Z-isomer and an E-isomer about the doublebond. Both gas phase and liquid phase processes are known to produce amixture of both the Z- and E-isomers, with the E-isomer predominating.The selectivity for the production of the Z-isomer can vary from about10% to about 23%, depending on the temperature, and choice of catalyst.The boiling point of the E-isomer at 1 atm is about −19° C., while theboiling point of the Z-isomer is about 9° C. For many uses, the E-isomeris preferred. So as to minimize yield losses in the form of thegenerally unwanted Z-isomer, it becomes necessary to either add anisomerization step to isomerize the Z-isomer to the E-isomer or add afluorination step to convert HFO-1234ze(Z) back to HFC-245fa.

The dehydrofluorination reaction according to embodiments of the presentdisclosure may result in compositions of HFO-1234ze(E), HFO-1225zc andHFO-1234yf that minimizes or eliminates the need for purification orseparation steps for removing excess quantities of HFO-1234yf orHFO-1225zc. In some cases, the composition may be azeotropic or nearazeotropic or include an azeotropic or near azeotropic composition. Byazeotropic compositions it is meant a constant-boiling mixture of two ormore substances that behave as a single substance. One manner tocharacterize an azeotropic composition is that the vapor produced bypartial evaporation or distillation of a liquid has the same compositionas the liquid from which it is evaporated or distilled (i.e., themixture distills/refluxes without compositional change).Constant-boiling compositions are characterized as azeotropic becausethey exhibit either a maximum or minimum boiling point, as compared withthat of the non-azeotropic mixture of the same compounds. An azeotropiccomposition will not fractionate within a refrigeration or airconditioning system during operation. Additionally, an azeotropiccomposition will not fractionate upon leakage from a refrigeration orair conditioning system. In the situation where one component of amixture is flammable, fractionation during leakage could lead to aflammable composition either within the system or outside of the system.

By a near-azeotropic composition it is meant to refer to a substantiallyconstant boiling liquid admixture of two or more compounds that behaveessentially as a single substance. One manner to characterize anear-azeotropic composition is that the vapor produced by partialevaporation or distillation of a liquid has substantially the samecomposition as the liquid from which it was evaporated or distilled,that is, the admixture distills/refluxes without substantiallycompositional change. Another manner to characterize a near-azeotropiccomposition is that the bubble point vapor pressure and the dew pointpressure of the composition at a particular temperature aresubstantially the same. In particular, a composition of the invention isnear-azeotropic if, after 50 weight percent (50%) of the composition isremoved, such as by evaporation or boiling off, the difference in vaporpressure, between the original composition and the composition remainingafter 50 weight percent of the original composition has been removed, isless than about 10 percent (10%).

In accordance with one embodiment of the instant invention, theinventive compositions have a flammability rating of A2L as determinedby ASHRAE Standard 34 and ASTM E681-09.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims.

Certain, dehydrofluorinations are known in the art, and are preferablyconducted in the vapor phase. The dehydrofluorination reaction may beconducted in any suitable reaction vessel or reactor, but it shouldpreferably be constructed from materials which are resistant to thecorrosive effects of hydrogen fluoride, such as nickel and its alloys,including Hastelloy, Monel, and Inconel, or vessels lined withfluoropolymers. These may be a single tube, or multiple tubes packedwith a dehydrofluorination catalyst.

Useful catalysts for the process include chromium-based catalysts suchas fluorinated chromium oxide, which catalyst may either be unsupported,or supported on a support such as activated carbon, graphite, fluoridegraphite, or alumina fluoride. The chromium catalyst may either be usedalone, or in the presence of a co-catalyst selected from nickel, cobalt,manganese or zinc salt. In one embodiment, a chromium catalyst is highsurface area chromium oxide, or chromium/nickel on alumina fluoride(Cr/Ni/AlF₃), the preparation of which is reported in European PatentEP486,333. In another embodiment, the catalyst is fluorinated Guignet'sgreen catalyst. Additional suitable catalysts include, but are notlimited to, JM 62-2 (chrome catalyst available from Johnson Matthey),LV(chrome catalyst available from Chemours), JM-62-3 (chrome catalystavailable from Johnson Matthey), and Newport Chrome (chrome catalystavailable from Chemours). The chromium catalysts are preferablyactivated before use, typically by a procedure whereby the catalyst isheated to from 350° C. to 400° C. under a flow of nitrogen for a periodof time, after which the catalyst is heated under a flow of HF andnitrogen or air for an additional period of time.

In one embodiment, the Guignet's Green of the fluoride-activatedGuignet's Green catalyst used in the present invention is made byreacting (fusing) boric acid with alkali metal dichromate at 500° C. to800° C., followed by hydrolysis of the reaction product, whereby saidGuignet's Green contains boron, alkali metal, and water of hydration.The usual alkali metal dichromates are the Na and/or K dichromates. Thereaction is typically followed by the steps of cooling the reactionproduct in air, crushing this solid to produce a powder, followed byhydrolysis, filtering, drying, milling and screening. The Guignet'sGreen is bluish green, but is known primarily as a green pigment,whereby the pigment is commonly referred to as Guignet's Green. Whenused as a catalyst, it is also referred to as Guignet's Green asdisclosed in U.S. Pat. No. 3,413,363. In U.S. Pat. No. 6,034,289, Cr₂O₃catalysts are disclosed as preferably being in the alpha form, andGuignet's Green is also disclosed as a commercially available greenpigment having the composition: Cr₂O₃ 79-83%, H₂O 16-18%, B₂O₅ 1.5 to2.7% (sentence bridging cols. 2 and 3) that can be converted to thealpha form (col. 3, I. 3). U.S. Pat. No. 7,985,884 acknowledges thepresence of alkali metal in the Guignet's Green in the composition ofGuignet's Green disclosed in Example 1: 54.5% Cr, 1.43% B, 3,400 ppm Na,and 120 ppm K. The disclosure of the foregoing patents and patentapplications is hereby incorporated by reference.

The physical shape of the catalyst is not critical and may, for example,include pellets, extrudates, powders, or granules. The fluorideactivation of the catalyst is preferably carried out on the final shapeof the catalyst.

In one embodiment, the instant invention relates to feeding a mixture ofHFC-245fa and at least about 10% by weight of the Z-isomer of HFO-1234zeto a dehydrofluorination reactor in the presence of an oxygen containinggas in order to suppress the formation of additional Z-isomer so thatthe HFC-245fa converted by dehydrofluorination produces substantiallyonly E-HFO-1234ze, HFO-1225zc and HFO-1234yf. Feeding less than about10% will result in some suppression of the formation of additionalZ-1234ze. Feeding greater than about 10% by weight of Z-1234ze simplyresults in the presence of additional material which must be separatedand recycled. The amount of Z-1234ze which is necessary to suppress thefurther formation of Z-isomer product is dependent to some extent onconversion. At 70% conversion of 245fa, about 10-11% Z-isomer in thefeed is required. At 80% conversion, about 13% Z-isomer in the feed isrequired

In one embodiment, the reaction vessel can be held at a temperature ofbetween 200° C. and 425° C. In another embodiment, the reaction vesselcan be held at a temperature of between 250° C. and 350° C. In yetanother embodiment, the reaction vessel can be held at a temperature ofbetween 275° C. and 325° C. or between 350° C. to 410° C.

The reaction pressure can be subatmospheric, atmospheric, orsuperatmospheric. In one embodiment, the reaction is conducted at apressure of from 14 psig to about 100 psig. In another embodiment, thereaction is conducted at a pressure of from 14 psig to about 60 psig. Inyet another embodiment, the reaction is conducted at a pressure of from40 psig to about 85 psig. In yet another embodiment, the reaction isconducted at a pressure of from 50 psig to 75 psig. In general,increasing the pressure in the reactor above atmospheric pressure willact to increase the contact time of the reactants in the process. Longercontact times will necessarily increase the degree of conversion in aprocess, without having to increase temperature.

Depending on the temperature of the reactor, and the contact time, theproduct mixture from the reactor will contain varying amounts ofunreacted HFC-245fa. In certain embodiment,E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, andHFO-1234yf may be separated from the Z-1,3,3,3-tetrafluoropropene,hydrogen fluoride, and any unreacted HFC-245fa, which are then recycledback to the reactor with additional HFC-245fa. Hydrogen fluoride may beremoved by scrubbing, by passing the reactor effluent through a solutionof aqueous caustic, or hydrogen fluoride may be removed by distillation.In particularly suitable embodiments, the composition formed from theprocess of the present disclosure includes both1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), HFO-1225zc and2,3,3,3-tetrafluoropropene (HFO-1234yf), which are not separated.

In one embodiment, the reactor feed is preheated in a vaporizer to atemperature of from about 30° C. to about 100° C. In another embodiment,the reactor feed is preheated in a vaporizer to a temperature of fromabout 30° C. to about 80° C.

In some embodiments, an inert diluent gas is used as a carrier gas forthe hydrochlorofluoropropane. In one embodiment, the carrier gas isselected from nitrogen, argon, helium, or carbon dioxide.

In one embodiment, the product mixture includes (on a mol basis) between0.01% to 1.00% HFO-1234yf, alternatively between 0.05% to 0.95%HFO-1234yf, alternatively between 0.10% to 0.90% HFO-1234yf,alternatively between 0.20% to 0.80% HFO-1234yf, alternatively between0.01% to 0.20% HFO-1234yf, alternatively between 0.10% to 0.30%HFO-1234yf, alternatively between 0.20% to 0.40% HFO-1234yf,alternatively between 0.30% to 0.50% HFO-1234yf, alternatively between0.30% to 0.40% HFO-1234yf, alternatively between 0.40% to 0.60%HFC-1234yf, alternatively between 0.50% to 0.70% HFO-1234yf,alternatively between 0.60% to 0.80% HFO-1234yf, alternatively between0.70% to 0.70% HFO-1234yf, alternatively between 0.80% to 1.00%HFO-1234yf. In another embodiment, the foregoing product mixturesfurther comprises (on a mole basis) HFO-1225zc wherein the HFO-1225zc ispresent in an amount equal to 10% of the HFO-1234yf.

In some embodiments, the fluoropropene composition additionallyoptionally comprises one or more of R-143a, R-152a, TFP, R-1233xf,R-1233zd(E), or R-1233zd(Z). In some embodiments, the sum total of theamounts of R-143a, R-152a, TFP, R-1233xf, R-1233zd(E), and R-1233zd(Z)is between 0.00001 mole percent and 2 mole percent, based on the totalfluoropropene composition. In one embodiment, the fluoropropenecomposition includes R-1233zd(E) in an amount of 0.7 mole percent to1.15 mole percent, based on the total heat transfer media. In oneembodiment, the fluoropropene composition includes R-1233zd(Z) in anamount of 0.05 mole percent to 0.25 mole percent, based on the totalheat transfer media. In one embodiment, the fluoropropene compositionincludes R-143a in an amount of 0.05 mole percent to 0.25 mole percent,based on the total fluoropropene composition.

In other embodiments, the fluoropropene composition optionally comprisesone or more of 1224yd, 1224zc, 1326mxz, 113, 32, 23, trifluoro propyne,356mff, 1326mxz, HFC-245fa and HFC-245cb. The amount of the foregoingcompounds can range from about 0.001 to about 1 mole %, about 0.001 toabout 0.9 and, in some cases, about 0.001 to about 0.7 mole %

In one particular embodiment, the sum total of the amounts 1224yd,1224zc, 1326mxz, 113, 32, 23, trifluoro propyne, 356mff, 1326mxz,HFC-245fa and HFC-245cb is between 0.001 mole percent and 2 molepercent, based on the total fluoropropene composition. The amount of theforegoing compounds can range from about 0.001 to about 0.1 mole %,about 0.001 to about 0.09 and, in some cases, about 0.001 to about 0.07mole %

In another particular embodiment, the inventive composition can comprisegreater than about 99 wt % HFO-1234ze(E) and, for example, 99.5 to99.99, 99.6 to 99.9 and in some cases about 99.7 to 99.99 wt %HFO-1234ze(E) with the remainder comprising HFO-1225zc and HFO-1234yf.The inventive compositions can also contain at least one additionalcompound selected from the group consisting of HFC-134a, 245cb, 236fa,1225ye isomers (e.g., E-1225ye and Z-1225ye), HFO-1234ze isomer (e.g.,HFO-1234ze(Z)), HFC-245fa, HFC-124, HCFC-114, trifluoropropyne, HFC-152aand HFO-1234 isomers including at least one member selected from thegroup consisting of HFO-1234zc, HFO-1234yc and HFO-1234ye. The totalcombined amount of HFO-1225zc, HFO-1234yf and the additional compound(s)can range from greater than 0 to less than about 1 wt. %, and forexample, greater than 0 to 0.3, greater than 0 to 0.1 and in some casesgreater than 0 to 0.01 mol %. A specific Example of the foregoingcomposition is shown in Table A below

TABLE A Components 134a 3.2 ppm 1225zc 1.5 ppm 1234yf 47 ppm 245cbCoelute with yf 236fa 1.1 ppm E-1234ze 99.98 E-1225ye 0.6 ppm 1234isomers* 6.1 ppm 245fa 20.5 ppm 124 4.6 ppm Z-1234ze 87 ppm 114 14 ppmtrifluoropropyne 1 ppm 152a 0.5 ppm Z-1225ye 4 ppm *Unknown includesHFO-1234zc, HFO-1234yc and HFO-1234ye

The fluoropropene composition may be useful in various applications. Inan embodiment, the fluoropropene composition may be used as arefrigerant. In some embodiments, the fluoropropene composition may beused as a replacement for older generation refrigerants (e.g., R404A,R502) to provide a more environmentally friendly composition. In someembodiments, the fluoropropene composition may be a hydrofluoro-olefincomposition. In an embodiment, the fluoropropene composition includesfrom 99 mole percent to 99.99 mole percent of 1,3,3,3-tetrafluoropropene(HFO-1234ze)(E) and from 0.0001 mole percent to 1.0 mole percent of1,1,3,3,3-pentafluoropropene (HFO-1225zc) and 2,3,3,3-tetrafluoropropene(HFO-1234yf). In another embodiment, the fluoropropene composition is anear azeotropic composition that is substantially free of HFO-1234ze(Z).By substantially free, it is meant that the fluoropropene compositioncontains less than about 1000 ppm, less than about 500 ppm and typicallyless than about 100 ppm, HFO-1234ze(Z).

In one embodiment, the foregoing inventive fluoropropene compositionscan be blended with other fluorochemicals. This embodiment of thepresent invention relates to a refrigerant composition comprising theinventive composition (e.g., HFO-1234ze(E), HFO-1225zc and HFO-1234yf)and at least one compound selected from the group consisting of:HFC-1234ye, HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a,HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa,HFC-365mfc, R1336mzz(E), propane, n-butane, isobutane, 2-methylbutane,n-pentane, cyclopentane, dimethylether, CF₃SCF₃, CO₂, CF₃I andcombinations thereof.

In one embodiment, the foregoing inventive fluoropropene compositionsare combined with at least one additional refrigerant comprising amember selected from the group consisting of R32, R125, R134, R134a,227ea, and R1336mzz(E). The amount of the at least one additionalrefrigerant can range from about 5 to about 95, about 50 to about 90 andin some cases about 60 to about 80 wt. % of the refrigerant composition.In one particular embodiment, the inventive fluoropropene compositionscan be employed as a source of HFO-1234ze for preparing R444, R446A/B,R447B, R448A, R450A, R456, R459A/B, R460A/B/C, R464A, 515A and 515B.

In some embodiments, the foregoing fluoropropene compositions may beused in a refrigeration system. One embodiment of a refrigeration systemincludes an evaporator, a condenser, a compressor, an expansion device,and a heat transfer media. The heat transfer media includes thefluoropropene composition. The heat transfer media can further compriseat least one lubricant including those suitable for use withrefrigeration or air-conditioning apparatus. Among these lubricants arethose conventionally used in compression refrigeration apparatusutilizing chlorofluorocarbon refrigerants. Such lubricants and theirproperties are discussed in the 1990 ASHRAE Handbook, RefrigerationSystems and Applications, chapter 8, titled “Lubricants in RefrigerationSystems”, pages 8.1 through 8.21, herein incorporated by reference.Lubricants of the present invention may comprise those commonly known as“mineral oils” in the field of compression refrigeration lubrication.Mineral oils comprise paraffins (i.e. straight-chain andbranched-carbon-chain, saturated hydrocarbons), naphthenes (i.e. cyclicor ring structure saturated hydrocarbons, which may be paraffins) andaromatics (i.e. unsaturated, cyclic hydrocarbons containing one or morerings characterized by alternating double bonds). Lubricants of thepresent invention further comprise those commonly known as “syntheticoils” in the field of compression refrigeration lubrication. Syntheticoils comprise alkylaryls (i.e. linear and branched alkyl alkylbenzenes),synthetic paraffins and naphthenes, silicones, and poly-alpha-olefins.Representative conventional lubricants of the present invention are thecommercially available BVM 100 N (paraffinic mineral oil sold by BVAOils), naphthenic mineral oil commercially available under the trademarkfrom Suniso® 3GS and Suniso® 5GS by Crompton Co., naphthenic mineral oilcommercially available from Pennzoil under the trademark Sontex® 372LT,naphthenic mineral oil commercially available from Calumet Lubricantsunder the trademark Calumet® RO-30, linear alkylbenzenes commerciallyavailable from Shrieve Chemicals under the trademarks Zerol® 75, Zerol®150 and Zerol® 500 and branched alkylbenzene, sold by Nippon Oil as HAB22.

In one embodiment, the lubricant component can comprise those which havebeen designed for use with refrigerants and are miscible with thefluoropropene compositions of the present invention under compressionrefrigeration and air-conditioning apparatus' operating conditions. Suchlubricants and their properties are discussed in “Synthetic Lubricantsand High-Performance Fluids”, R. L. Shubkin, editor, Marcel Dekker,1993. Such lubricants include, but are not limited to, polyol esters(POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkyleneglycols (PAGs) such as RL-488A from Dow (Dow Chemical, Midland, Mich.),and polyvinyl ethers (PVEs).

Lubricants of the present invention are selected by considering a givencompressor's requirements and the environment to which the lubricantwill be exposed. The amount of lubricant can range from about 1 to about50, about 1 to about 20 and in some cases about 1 to about 3 weightpercent of a refrigerant composition. In one particular embodiment, theforegoing refrigerant compositions are combined with a PAG lubricant forusage in an automotive A/C system having an internal combustion engine.In another particular embodiment, the foregoing refrigerant compositionsare combined with a POE lubricant for usage in an automotive A/C systemhaving an electric or hybrid electric drive train.

In one embodiment, a refrigerant composition comprises the inventivenear azeotropic composition, at least one lubricant and at least oneadditive which can improve the refrigerant and air-conditioning systemlifetime and compressor durability are desirable. In one aspect of theinvention, the foregoing refrigerant compositions comprise at least onemember selected from the group consisting of acid scavengers,performance enhancers, and flame suppressants.

In another embodiment, the fluoropropene composition may be used in aprocess to transfer heat. The process may include providing an articleand contacting the article with a heat transfer media including thefluoropropene composition. In some embodiments, the article may includeelectrical equipment (e.g., circuit board, computer, display,semiconductor chip, or transformer), a heat transfer surface (e.g., heatsink), or article of clothing (e.g., a body suit).

In another embodiment, the fluoropropene composition may be used in aprocess for treating a surface. The process may include providing asurface having a treatable material deposited thereon and contacting thesurface with a treatment composition including the fluoropropenecomposition. In some embodiments, the treatment composition maysubstantially dissolve the treatable material.

In another embodiment, the fluoropropene composition may be used in aprocess for forming a composition. The process includes providing asolute and contacting the solute with a solvent including thefluoropropene composition. In some embodiments, the fluoropropenecomposition may substantially dissolve the solute.

In another embodiment, the present invention relates to blowing agentcompositions comprising the fluoroolefin-containing compositions (e.g.,near azeotropic containing compositions), as described herein for use inpreparing foams. In other embodiments the invention provides foamablecompositions, and preferably polyurethane and polyisocyanate foamcompositions, and method of preparing foams. In such foam embodiments,one or more of the present fluoroolefin-containing compositions areincluded as a blowing agent in foamable compositions, which compositionpreferably includes one or more additional components capable ofreacting and foaming under the proper conditions to form a foam orcellular structure. Any of the methods well known in the art, such asthose described in “Polyurethanes Chemistry and Technology,” Volumes Iand II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y.,which is incorporated herein by reference, may be used or adapted foruse in accordance with the foam embodiments of the present invention.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition afluoroolefin-containing composition of the present invention; and (b)reacting the foamable composition under conditions effective to form afoam.

Another embodiment of the present invention relates to the use of thefluoroolefin-containing compositions as described herein (e.g., nearazeotropic compositions of HFO-1234ze(E), HFO-1225zc and HFO-1234yf),for use as propellants in sprayable compositions. Additionally, thepresent invention relates to a sprayable composition comprising thefluoroolefin-containing compositions as described herein. The activeingredient to be sprayed together with inert ingredients, solvents andother materials may also be present in a sprayable composition.Preferably, the sprayable composition is an aerosol. Suitable activematerials to be sprayed include, without limitations, cosmeticmaterials, such as deodorants, perfumes, hair sprays, cleaners, andpolishing agents as well as medicinal materials such as anti-asthma andanti-halitosis medications.

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a fluoroolefin-containingcomposition as described herein to active ingredients in an aerosolcontainer, wherein said composition functions as a propellant.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistsof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole. Thetransitional phrase “consisting essentially of” is used to define acomposition, method that includes materials, steps, features,components, or elements, in addition to those literally disclosedprovided that these additional included materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention, especially the mode ofaction to achieve the desired result of any of the processes of thepresent invention. The term ‘consisting essentially of’ occupies amiddle ground between “comprising” and ‘consisting of’.

In the foregoing combinations of inventive embodiments, the compositionscan comprise, consist essentially of or consist of HFO-1234ze(E),HFO-1225zc and HFO-1234yf.

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

Example 1 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An Inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Johnson Mathey) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 1.

TABLE 1 % Z-ze added 0 7.5 10.9 Incoming compos 100/0 92.5/7.5 89/11245fa conversion (%) 71.2 69.3 72 Z-ze in product (%) 10.7 10.3 11.2 %recovered 245fa 28.8 28.4 24.9 % E-ze 60.5 60.3 63.9 % yield E-ze 60.565.3 71.7 % selectivity E-ze 85 94.2 99.7

Example 2

Example 2 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An Inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Guignet's green) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 2.

TABLE 2 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 69.9 71.8 Z-ze in product (%) 10.7 10.9 % recovered 245fa 30.1 25.1% E-ze 59.2 64 % yield E-ze 59.2 71.9 % selectivity E-ze 84.7 100

Example 3

Example 3 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Johnson Mathey) which had been prepared as follows. Chromicoxide in extrudate form, which was crushed and sieved to 12/20 mesh.After charging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued, and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 3.

TABLE 3 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 73 71.3 Z-ze in product (%) 11.4 11.0 % recovered 245fa 27.0 25.5 %E-ze 61.6 63.5 % yield E-ze 61.6 72.5 % selectivity E-ze 84 100

Example 4

Example 4 demonstrates the dehydrofluorination of 245fa over Cr₂O₃ inthe presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of Cr₂O₃catalyst (Newport Cr) which had been prepared as follows. Chromic oxidein extrudate form, which was crushed and sieved to 12/20 mesh. Aftercharging the reactor tube, the temperature of the catalyst bed wasraised to 300° C. and purged with nitrogen (30 cc/min) for 200 minutes.Then the flow of nitrogen was reduced to 60 cc/min and HF was fed at 20cc/min for 60 minutes. The temperature was increase to 325° C. for 300minutes. The flow of nitrogen was then lowered to 30 cc/min and the flowof HF was raised to 30 cc/min for 30 minutes. The flow of nitrogen wasthen lowered to 12 cc/min and the flow of HF was raised to 48 cc/min for60 minutes. The flow of nitrogen was then discontinued and the flow ofHF was raised to 48 cc/min for 30 minutes. The reactor temperature wasthen decreased to 250° C. for 30 minutes. Afterwards HF was turned offand the reactor was purged with 30 cc/min of nitrogen. The reactortemperature was then stabilized at 300° C., the flow of nitrogen wasturned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂ with varying amounts ofZ-1234ze, was fed at 1.44 ml/hr. Contact time in the reactor was 45seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part of the reactoreffluent was passed through a series of valves and analyzed by GCMS.Amounts for Z-1234ze, 245fa and E-1234ze are expressed as mole percent.Results are summarized in Table 4.

TABLE 4 % Z-ze added 0 10.7 Incoming compos 100/0 89.3/10.7 245faconversion (%) 72.2 70.2 Z-ze in product (%) 10.4 10.5 % recovered 245fa27.8 26.6 % E-ze 61.8 62.9 % yield E-ze 61.8 70.4 % selectivity E-ze85.5 100

Example 5

Example 5 demonstrates the dehydrofluorination of 245fa over fluoridedalumina in the presence of Z-HFC-1234ze.

An inconel tube (½ inch OD) is filled with 10 cc (6.1 gm) of Al₂O₃catalyst (purchased from Sigma-Aldrich). Al₂O₃ in extrudate form, whichis crushed and sieved to 12/20 mesh. After charging the reactor tube,the temperature of the catalyst bed is raised to 300° C. and purged withnitrogen (30 cc/min) for 200 minutes. Then the flow of nitrogen isreduced to 60 cc/min and HF is fed at 20 cc/min for 60 minutes. Thetemperature is increase to 325° C. for 300 minutes. The flow of nitrogenis then lowered to 30 cc/min and the flow of HF is raised to 30 cc/minfor 30 minutes. The flow of nitrogen is then lowered to 12 cc/min andthe flow of HF is raised to 48 cc/min for 60 minutes. The flow ofnitrogen is then discontinued, and the flow of HF is raised to 48 cc/minfor 30 minutes. The reactor temperature is then decreased to 250° C. for30 minutes. Afterwards HF is turned off and the reactor is purged with30 cc/min of nitrogen. The reactor temperature is then stabilized at300° C., the flow of nitrogen is turned off, and either CF₃CH₂CHF₂, orCF₃CH₂CHF₂ with varying amounts of Z-1234ze, is fed at 1.44 ml/hr.Contact time in the reactor is 45 seconds.

The CF₃CH₂CHF₂ is vaporized at 50° C. Part of the reactor effluent ispassed through a series of valves and analyzed by GCMS. Amounts forZ-1234ze, 245fa and E-1234ze are expressed as mole percent. Results aresummarized in Table 5.

TABLE 5 % Z-ze added 0 10.9 Incoming compos 100/0 89/11 245fa conversion(%) 70 71 Z-ze in product (%) 11 11 % recovered 245fa 30 29 % E-ze 59 58% yield E-ze 59 65 % selectivity E-ze 84.3 100

Example 6

Table 6 discloses the reaction products of the dehydrofluorination of245fa over various catalysts in the presence of Z-HFC-1234ze (in mol %).

TABLE 6 Catalyst Unknown 143a 152a TFP 1234yf 1233xf JM 62-2 0.15% 0.13%0.00% 0.01% 0.35% 0.03% LV 0.28% 0.14% 0.03% 0.02% 0.04% 0.00% JM-62-30.28% 0.14% 0.02% 0.02% 0.24% 0.04% Newport-Chrome 0.12% 0.13% 0.00%0.00% 0.92% 0.00% Catalyst E-1233zd Z-1233zd Z-1234ze E-1234ze E +Z-1234ze JM 62-2 0.88% 0.13% 11.17%  87.13% 98.3% LV 1.03% 0.15% 10.9%87.4% 98.3% JM-62-3 0.92% 0.14%  11% 87.2% 98.2% Newport-Chrome 0.92%0.11% 10.5% 87.3% 97.8%

An inconel tube (½ inch OD) was filled with 10 cc (8 gm) of catalyst(see Table 6). After charging the reactor tube, the temperature of thecatalyst bed was raised to 300° C. and purged with nitrogen (30 cc/min)for 200 minutes. Then the flow of nitrogen was reduced to 60 cc/min andHF was fed at 20 cc/min for 60 minutes. The temperature was increase to325° C. for 300 minutes. The flow of nitrogen was then lowered to 30cc/min and the flow of HF was raised to 30 cc/min for 30 minutes. Theflow of nitrogen was then lowered to 12 cc/min and the flow of HF wasraised to 48 cc/min for 60 minutes. The flow of nitrogen was thendiscontinued, and the flow of HF was raised to 48 cc/min for 30 minutes.The reactor temperature was then decreased to 250° C. for 30 minutes.Afterwards HF was turned off and the reactor was purged with 30 cc/minof nitrogen. The reactor temperature was then stabilized at 300° C., theflow of nitrogen was turned off, and either CF₃CH₂CHF₂, or CF₃CH₂CHF₂with 10.5-11% of Z-1234ze, was fed at 1.44 ml/hr. Contact time in thereactor was 45 seconds. The CF₃CH₂CHF₂ was vaporized at 50° C. Part ofthe reactor effluent was passed through a series of valves and analyzedby GCMS. Amounts for Z-1234ze, 134a, 152b, TFP, 1234yf, 1233xf,E-1233zd, Z-1233zd and E+Z-1234ze are expressed as mole percent. Resultsare summarized in Table 6. A grab sample was also taken for off-lineGCMS analysis. It was detected that the Unknowns of Table 6 (some ofthem coelute with other peaks) contained 236fa, 1225zc, 1225ye (E andZ), 1234ye, 1234zc and trifluoropropyne.

While any GCMS equipment, method and parameters, which are suitable fordetecting the compounds that may be present in the inventivecompositions, can be employed, one suitable method uses a single RTX-1column.

Example 7

Table 7 shows the near azeotropic characteristic of variouscompositions, which can be produced by the method of the presentinvention, by measuring Delta P of vapor pressure in terms of percentchange. Delta P vapor pressure is the vapor pressure change at −25° C.after a 50% vapor leak wherein 50% of the vapor is removed.

TABLE 7 1234zeE/1234yf wt % Delta P % 99/1 0.45 99.1/0.9 0.40 99.2/0.80.36 99.3/0.7 0.31 99.4/0.6 0.28 99.5/0.5 0.22 99.6/0.4 0.19 99.7/0.30.13 99.8/0.2 0.09 99.9/0.1 0.04 99.91/0.09 0.04 99.95/0.05 0.0399.96/0.04 0.02 99.97/0.03 0.01 99.98/0.02 0.009 99.99/0.01 0.00599.9987/.0013  0.001

Example 8

Table 8 shows the cooling performance of various near azeotropiccompositions, which can be produced by the method of the presentinvention, by comparing cooling capacity and energy efficiency (COP) toHFO-1234ze(E). The data are based on the following conditions.

T_condenser=47.0 deg C

T_evaporator=7.0 deg C

subcool=12.0 K

superheat=3.0 K

compressor efficiency=0.7

Average Heat Exchanger Temperature Set Points

Superheat is included in refrigeration effect

cooling load=1.0 tonnes

compressor displacement=0.1 (m{circumflex over ( )}3/min)

TABLE 8 Capacity COP Cooling Rel to Rel to Capacity 1234ze 1234ze Mol %(kJ/m3) (%) COP (%) 1234ze 100 2111 100.0% 4.402 100.0% 1234ze/1234yf99.9/0.1 2112 100.0% 4.402 100.0% 1234ze/1234yf 99.7/0.3 2114 100.1%4.402 100.0% 1234ze/1234yf 99.5/0.5 2116 100.2% 4.402 100.0%1234ze/1234yf 99.1/0.9 2120 100.4% 4.401 100.0%

Example 8 illustrates that the inventive near azeotropic compositionsare effective for use as refrigerants and have refrigeration propertiesat least equivalent to HFO-1234ze(E).

Example 9

An inconel tube (½ inch {13 mm} OD) was filled with 5 cc (3.9 gm) ofCr₂O₃ catalyst (Louisville Cr) which was activated as described inExample 6. After activation, the flow of nitrogen was turned off, andthe reactor temperature was set to 400° C. A flow of air (4 vol % O2)and either CF₃CH₂CHF₂ (245fa alone), or CF₃CH₂CHF₂ with 13.3 mole %(corresponding to 11.5 wt %) of Z-1234ze, was fed at 0.67 ml/hr. Contacttime in the reactor was 38 seconds. The CF₃CH₂CHF₂ was vaporized at 50°C. Part of the reactor effluent was passed through a series of valvesand analyzed by GCMS. After 72 hours the flow of oxygen was stopped andthe reactions were continued for another 72 hours in the absence of anoxygen containing gas. The catalysts started deactivating at a totaltime of about 120 hours for the reaction run with 245fa alone and at atotal time of about 136 hours for the reaction run with 245fa containingZ-1234ze. Results are summarized in the following table with the amountsfor Z-1234ze, 245fa and E-1234ze being expressed as mole percent:

TABLE 9 % Z-ze added 0 0 13.3 13.3 oxygen yes no yes no Incomingcomposition 100/0 100/0 86.7/13.3 86.7/13.3 245fa conversion (%) 96.189.7 95.8 89.5 Z-ze in product (%) 22.9 21.1 22.7 20.8 % recovered 245fa3.9 10.4 3.8 9.3 % E-ze 73.2 68.6 73.5 69.9 % yield E-ze 73.2 60.2 85.080.9 % selectivity E-ze 76.2 76.4 88.7 90.2

Example 10

Table 10 shows the cooling performance of various refrigerantcompositions comprising HFO-1234ze(E), HFO-1225zc and HFO-1234yf, whichcan be produced by the method of the present invention, by comparingcooling capacity and energy efficiency (COP) to HFO-1234ze(E). The dataare based on the following conditions

TABLE 10 ThermPy Results delta P % - CAP_c 50% mass fluid(kJ/m{circumflex over ( )}3) COP_c leak at −25° C. R-1234zeE 2111.44.402 0.000 _R-1234yf_R-1225zc_R- 2112.4 4.402 −0.023 1234zeE_W =_0.0_0.005_0.995 _R-1234yf_R-1225zc_R- 2113.3 4.402 −0.089 1234zeE_W =_0.00125 _0.00375_0.995 _R-1234yf_R-1225zc_R- 2114.2 4.402 −0.1581234zeE_W = _0.0025_0.0025_0.995 _R-1234yf_R-1225zc_R- 2115.2 4.402−0.220 1234zeE_W = _0.00375_0.00125_0.995 _R-1234yf_R-1225zc_R- 2116.14.402 −0.285 1234zeE_W = _0.005_0.0_0.995 R-515B 2100.4 4.393 −0.001_R-1225zc_R-1234yf_R-1234zeE_R- 2104.6 4.392 −0.255 227ea_W =_0.0_0.00456_0.90644_0.089 _R-1225zc_R-1234yf_R-1234zeE_R- 2103.7 4.392−0.197 227ea_W = _0.00114_0.00342_0.90644_0.089_R-1225zc_R-1234yf_R-1234zeE_R- 2102.9 4.392 −0.139 227ea_W =_0.00228_0.00228_0.90644_0.089 _R-1225zc_R-1234yf_R-1234zeE_R- 2102.14.392 −0.080 227ea_W = _0.00342_0.00114_0.90644_0.089_R-1225zc_R-1234yf_R-1234zeE_R- 2101.3 4.393 −0.021 227ea_W =_0.00456_0.0_0.90644_0.089 R-515A 2096.1 4.389 −0.003_R-1225zc_R-1234yf_R-1234zeE_R- 2100.1 4.389 −0.245 227ea_W =_0.0_0.0044_0.8756_0.12 _R-1225zc_R-1234yf_R-1234zeE_R- 2099.3 4.389−0.190 227ea_W = _0.0011_0.0033_0.8756_0.12_R-1225zc_R-1234yf_R-1234zeE_R- 2098.5 4.389 −0.134 227ea_W =_0.0022_0.0022_0.8756_0.12 _R-1225zc_R-1234yf_R-1234zeE_R- 2097.7 4.389−0.078 227ea_W = _0.0033_0.0011_0.8756_0.12_R-1225zc_R-1234yf_R-1234zeE_R- 2096.9 4.389 −0.022 227ea_W =_0.0044_0.0_0.8756_0.12 R-450A 2465.1 4.394 −1.86_R-1225zc_R-1234yf_R-1234zeE_R- 2467.7 4.394 −1.92 134a_W =_0.0_0.0029_0.5771_0.42 _R-1225zc_R-1234yf_R-1234zeE_R- 2467.2 4.394−1.90 134a_W = _0.00073_0.00218_0.5771_0.42_R-1225zc_R-1234yf_R-1234zeE_R- 2466.8 4.394 −1.89 134a_W =_0.00145_0.00145_0.5771_0.42 _R-1225zc_R-1234yf_R-1234zeE_R- 2466.34.394 −1.87 134a_W = _0.00218_0.00073_0.5771_0.42_R-1225zc_R-1234yf_R-1234zeE_R- 2465.9 4.394 −1.86 134a_W =_0.0029_0.0_0.5771_0.42 Refrigerant A 2276.7 4.421 −0.084_R-1225zc_R-1234yf_R-1234zeE_R- 2279.3 4.421 −0.199 134_W =_0.0_0.00315_0.62685_0.37 _R-1225zc_R-1234yf_R-1234zeE_R- 2278.9 4.421−0.175 134_W = _0.00079_0.00236_0.62685_0.37_R-1225zc_R-1234yf_R-1234zeE_R- 2278.5 4.421 −0.151 134_W =_0.00157_0.00157_0.62685_0.37 _R-1225zc_R-1234yf_R-1234zeE_R- 2278.14.421 −0.127 134_W = _0.00236_0.00079_0.62685_0.37_R-1225zc_R-1234yf_R-1234zeE_R- 2277.7 4.421 −0.103 134_W =_0.00315_0.0_0.62685_0.37 Refrigerant B 1885.4 4.409 −5.82_R-1225zc_R-1234yf_R-1234zeE_R-1336mzzE_R- 1888.8 4.408 −6.10 227ea_W =_0.0_0.00393_0.78307_0.17_0.043_R-1225zc_R-1234yf_R-1234zeE_R-1336mzzE_R- 1888.1 4.408 −6.04 227ea_W =_0.00098_0.00295_0.78307_0.17_0.043_R-1225zc_R-1234yf_R-1234zeE_R-1336mzzE_R- 1887.4 4.408 −5.98 227ea_W =_0.00197_0.00197_0.78307_0.17_0.043_R-1225zc_R-1234yf_R-1234zeE_R-1336mzzE_R- 1886.7 4.408 −5.91 227ea_W =_0.00295_0.00098_0.78307_0.17_0.043_R-1225zc_R-1234yf_R-1234zeE_R-1336mzzE_R- 1886.1 4.408 −5.85 227ea_W =_0.00393_0.0_0.78307_0.17_0.043 R-448A 4718.7 4.214 −14.4_R-1225zc_R-1234yf_R-1234zeE_R-125_R-134a_R- 4719 4.214 −14.3 32_W =_0.0_0.20035_0.06965_0.26_0.21_0.26_R-1225zc_R-1234yf_R-1234zeE_R-125_R-134a_R- 4719 4.214 −14.3 32_W =_9e−05_0.20026_0.06965_0.26_0.21_0.26_R-1225zc_R-1234yf_R-1234zeE_R-125_R-134a_R- 4719 4.214 −14.3 32_W =_0.00017_0.20017_0.06965_0.26_0.21_0.26_R-1225zc_R-1234yf_R-1234zeE_R-125_R-134a_R- 4719 4.214 −14.4 32_W =_0.00026_0.20009_0.06965_0.26_0.21_0.26_R-1225zc_R-1234yf_R-1234zeE_R-125_R-134a_R- 4718.9 4.214 −14.4 32_W =_0.00035_0.2_0.06965_0.26_0.21_0.26 T_condenser = 47.0° C. T_evaporator= 7.0° C. subcool = 12.0 K superheat = 3.0 K compressor efficiency = 0.7Average Heat Exchanger Temperature Set Points Superheat is included inrefrigeration effect. cooling load = 3.517 kW compressor displacement =0.00283168438736 (m{circumflex over ( )}3/min)

Note that not all the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

While the invention has been described with reference to a preferredembodiment, it will be understood by those skilled in the art thatvarious changes may be made, and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

What is claimed is:
 1. A refrigerant composition comprisingZ-1,3,3,3-tetrafluoropropene, E-1,3,3,3,-tetrafluoropropene,1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene and at leastone member selected from the groups consisting of: (a) R-143a, R-152a,TFP, R-1233xf, R-1233zd(E), R-1233zd(Z) 1224yd, 1224zc, 1326mxz, 113,32, 23, trifluoropropyne, 1326mxz, HFC-245cb 1234zc, 1234yc, 1234ye,134a, 1225ye (Z and E), 114, 124, and 236fa, (b) R-143a, R-152a, TFP,R-1233xf, R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32,23, trifluoropropyne, 1326mxz, and HFC-245cb, and (c) HFC-1234ye,HFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, R1336mzz(E), propane,n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF3SCF3, CO2, and CF3I; and wherein the refrigerantcomposition comprises greater than about 99 wt. %E-1,3,3,3-tetrafluoropropene and less than about 1,000 ppm ofZ-1,3,3,3-tetrafluoropropene.
 2. The refrigerant of claim 1 wherein2,3,3,3-tetrafluoropropene and 1,1,3,3,3-pentafluoropropene both beingpresent and wherein the total amount of 1,1,3,3,3-pentafluoropropene and2,3,3,3-tetrafluoropropene is less than 1.0 mol %.
 3. The refrigerant ofclaim 1 wherein the 2,3,3,3-tetrafluoropropene is present in an amountof 0.1 to 0.9 mol %.
 4. The refrigerant of claim 1 wherein the2,3,3,3-tetrafluoropropene is present in an amount of 0.2 to 0.4 mol %.5. The refrigerant of claim 1 wherein the 2,3,3,3-tetrafluoropropene ispresent in an amount of 0.3 to 0.4 mol %.
 6. The refrigerant of claim 1wherein the member comprises one or more of R-143a, R-152a, TFP,R-1233xf, R-1233zd(E), R-1233zd(Z) 1224yd, 1224zc, 1326mxz, 113, 32, 23,trifluoro propyne, 356mff, 1326mxz, HFC-245cb 1234zc, 1234yc, 1234ye,134a, 1225ye (Z and E), 114, 124, and 236fa.
 7. The refrigerant of claim6 wherein the sum total of the amounts of R-143a, R-152a, TFP, R-1233xf,R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32, 23,trifluoro propyne, 356mff, 1326mxz, and HFC-245cb is between 0.001 molepercent and 2 mole percent, based on the total fluoropropenecomposition.
 8. The refrigerant of claim 1 wherein the refrigerantincludes R-1233zd(E) in an amount of 0.7 mole percent to 1.15 molepercent, based on the total fluoropropene composition.
 9. Therefrigerant of claim 1 wherein the refrigerant includes R-1233zd(Z) inan amount of 0.05 mole percent to 0.25 mole percent, based on the totalfluoropropene composition.
 10. The refrigerant of claim 1 wherein therefrigerant includes R-143a in an amount of 0.05 mole percent to 0.25mole percent, based on the total fluoropropene composition.
 11. Therefrigerant of claim 1 wherein the refrigerant is near azeotropic. 12.The refrigerant of claim 1 wherein the member comprises at least onemember selected from the group consisting of HFC-1234ye, HFC-1243zf,HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161,HFC-227ea, HFC-236ea, HFC-236fa, HFC 365mfc, R1336mmz(E), propane,n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane,dimethylether, CF3SCF3, CO2, and CF3I.
 13. A process for transferringheat, comprising: providing an article; contacting the article with aheat transfer media; wherein the heat transfer media comprises thecomposition of claim
 1. 14. A refrigeration system, comprising: anevaporator; a condenser; a compressor; an expansion device; and a heattransfer media; wherein the heat transfer media comprises thecomposition of claim
 1. 15. The refrigerant of claim 1 wherein themember comprises one or more of R-143a, R-152a, TFP, R-1233xf,R-1233zd(E), R-1233zd(Z), 1224yd, 1224zc, 1326mxz, 113, 32, 23,trifluoropropyne, 1326mxz and HFC-245cb.
 16. The refrigerant of claim 1further comprising at least one lubricant.
 17. The refrigerant of claim1 wherein the member comprises of at least one of R-143a, R-152a,R-1233xf, R-1233zd(E), 1224yd, trifluoropropyne, HFC-245cb 1234zc, 134a,1225ye (Z and E), 114, 124, and 236fa.
 18. The refrigerant of claim 1wherein the member comprises at least one of R-143a, R-152a, TFP,R-1233xf, R-1233zd(E), 1224yd, 32, trifluoropropyne, and HFC-245cb. 19.The refrigerant of claim 1 wherein the member comprises at least one ofHFC-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a,HFC-227ea, HFC-236fa, R1336mzz(E), propane, n-butane, isobutane,2-methylbutane, n-pentane, cyclopentane, dimethylether, and CO₂.
 20. Therefrigerant of claim 1 further comprising HFC-245fa.